Patent GB-824381-A (GB)
Title: Oil-soluble metal containing compositions and process for making them
Inventor: MASTIN THOMAS WILLIAM
IPC: C10M159/22
Filed: 1956-12-31
Abstract: Oil-soluble metallic phenate compositions, containing large amounts of metal, are prepared by mixing in an organic liquid medium (a) an alkylated monohydroxy phenol, (b) an oil-soluble, metal-free, non-tautomeric, polar, neutral or basic compound present in an amount greater than that of (a) on a weight basis, and (c) at least two equivalents of a basic inorganic metal compound per equivalent of (a).  The mixture, which may be in a mineral oil, is heated to drive off any water that may be present and is then treated with an acidic gas having an ionization constant greater than that of (a) until the titratable basicity of the mixture has been substantially reduced. Compound (a) is an alkyl phenol where the alkyl groups contain at least 3 carbon atoms and where the ring may also bear cycloalkyl, halogen, nitro or alkoxy substituents.  An aldehyde condensate of one of these phenols may also be used.  Compound (b) may be a long-chain ester, amine, ether, alcohol, sulphoxide or sulphide such as glyceryl acetate or oleate, octadecenyl or oleyl alcohol, tridecyl alcohol, N-octadecyl propylene diamine or sperm oil.  Compound (c) may be a Group I or II metal oxide, hydroxide, sulphide or hydrosulphide such as barium oxide.  The composition is prepared preferably in a mineral oil, although other organic liquids, such as low molecular weight polyethylene or polypropylene, toluene, xylene, kerosene or trichlorethylene, may be used.  The mixture is then treated, normally above 100 DEG  C., with an acidic gas such as carbon dioxide until it is substantially neutral.  In the examples, the phenol, non-acidic polar compound and water are heated in a mineral oil at 70 DEG  C. and the inorganic compound then added.  In the examples 1-11, in which the inorganic compound is barium oxide and the acidic gas carbon dioxide, except in Example (4), where sulphur dioxide is used, and Example (5), where lithium hydroxide is used, di-isobutyl phenols are heated with (1) polyisobutylene sulphoxide, (2) oleyl alcohol, (7) sperm oil, (9) sulphurized sperm oil, and (10) N-octadecyl propylene diamine; (3) tert.-butyl phenols are heated with oleyl alcohol; heptyl phenols are heated with oleyl alcohol; heptyl phenols are heated with (4); (5) oleyl alcohol; and (6) polyisobutylphenoxyethanol; a heptyl phenolformaldehyde condensate is heated with (8) sperm oil; and (11) N-octadecyl propylenediamine.ALSO:Oil-soluble metallic phenate compositions, containing large amounts of metal, are prepared by mixing in an organic liquid medium (a) an alkylated monohydroxyphenol as defined below, (b) an oil-soluble, metal-free, non-tautomeric, polar, neutral or basic compound present in an amount greater than that of (a) on a weight basis, and (c) at least two equivalents of a basic inorganic metal compound per equivalent of (a); heating the mixture to drive off any water that may be present and then treating the water-free mixture with an acidic gas having an ionization constant greater than that of (a) until the titratable basicity of the mixture has been substantially reduced.  The compound (a) is a phenol having at least one alkyl or cycloalkyl group which will yield an oil-soluble metal phenate and wherein the alkyl group contains at least three carbon atoms.  Typical substituents include isopropyl, tert.-butyl, 2-methylamyl, isoheptyl, di-isobutyl, n-decyl, tetrapropyl, octadecyl and polyisobutyl.  The ring may also be substituted by cycloalkyl groups such as cyclohexyl and methylcyclohexyl, while halogen, nitro or alkoxy groups may also be present.  The compound (a) may also be an aldehyde condensation product of one of the alkylated phenols. Compound (b) is characterized by having both an oil-solubilizing substituent, such as a long hydrocarbon chain, and a polar substituent such as an ester, amine, hydroxy sulphoxy, ether or sulphide group. Glyceryl oleate or stearate, octadecenyl or oleyl alcohol, tridecyl alcohol, N-octadecyl-propylene diamine and sperm oil are amongst those compounds which may be used.  Compound (c) may be a Group I or II metal oxide, hydroxide, sulphide or hydrosulphide and barium oxide is preferred.  The composition is preferably prepared in a mineral oil although other liquids such as low molecular weight polyethylene and polypropylene, toluene, xylene, kerosene and trichlorethylene may be used.  The mixture is then treated, normally at above 100 DEG C., with an acidic gas such as sulphur dioxide or trioxide, carbon dioxide or disulphide, hydrogen sulphide or nitric oxide; carbon dioxide is normally preferred.  The treatment with acidic gas is normally continued until the oil mixture is substantially neutral.  The resulting product, when filtered, may be used as a stabilizer for polymerized olefinically unsaturated compounds, particularly polyvinyl chloride compositions (see Group IV (a)).  In the examples the phenol, non-acidic polar compound, and water are heated in a mineral oil at 70 DEG  C. and the inorganic compound then added.  The per cent sulphate ash, meutralisation number and metal ratio (the ratio of number of equivalents of metal to number of equivalents of phenol in the mixture) are given for each sample. The metal ratio is approximately 6:1 in each case.  In the Examples 1-11, in which the inorganic compound is barium oxide and the gas carbon dioxide except in Example 4 where sulphur dioxide is used and Example 5 where lithium hydroxide is used, di-isobutyl phenols are heated with (1) polyisobutylene sulphoxide, (2) oleyl alcohol, (7) sperm oil, (9) sulphurized sperm oil and (10) N-octadecyl-propylene diamine; (3) tert.-butyl phenols are heated with oleyl alcohol; heptyl phenols are heated with (4), (5) oleyl alcohol, and (6) polyisobutylphenoxyethanol; a heptyl phenolformaldehyde condensate is heated with (8) sperm oil, and (11) N-octadecyl-propylene diamine.ALSO:Polymers of olefinically unsaturated compounds are stabilized by mixing them with an oil soluble metallic phenate composition, prepared (see Group IV (b)), by mixing in an organic liquid medium (a) an alkylated mono hydroxy phenol, (b) and oil soluble, metal free, non-tautomeric, polar neutral or basic compound present in an amount greater than that of (a) on a weight basis, and (c) at least 2 equivalents of a basic inorganic metal compound per equivalent of (a).  The mixture, (which is preferably in a mineral oil), is heated to drive off any water, which may be present, and then treated with an acidic gas having an ionization constant greater than that of (a) until the titratable basicity of the mixture has been substantially reduced. Component (a) may also be an aldehyde condensate with an alkyl phenol, component (b) may be a long chain alcohol, ester, amine, ether, sulphide or sulphoxide, the inorganic compound is preferably barium oxide and the acidic gas carbon dioxide.  The compositions may be used to stabilize polyvinyl chloride, polyethylene, polyisobutylene, polystyrene, polyvinylidene chloride; copolymers of vinyl chloride with vinyl acetate, ethylene, diethyl fumarate, dibutyl maleate and vinylidene chloride; copolymers of isobutylene with isoprene, butadiene and styrene; copolymers of vinylidene chloride with diethyl maleate, methyl acrylate, acrylamide and vinyl acetate.  In the examples, (12) a stabilizer in mineral oil prepared from diisobutyl phenols, sperm oil and barium oxide is milled with polyvinyl chloride, dioctyl phthalate and cadmium naphthenate, (13) a stabilizer in mineral oil prepared from a heptyl phenol-formaldehyde condensate, sperm oil and barium oxide is milled with polyvinyl chloride, dioctyl phthalate, epoxidized soybean oil and cadmium laurate; (14) a stabilizer in mineral oil prepared from di-isobutyl phenols, oleyl alcohol and barium oxide is milled with polyvinyl chloride, dioctyl phthalate and cadmium laurate.  These sheets show no colour change after heating at 190 DEG  C. for 75 minutes.